Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
  • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

Definitions

• the present invention relates to the use of certain water-soluble, hydrophobically modified linear polysaccharide ethers, in particular cellulose ether derivatives, as deposition enhancers for agriculturally active ingredients in aqueous solutions. It further relates to compositions comprising said cellulose ether derivatives and at least one agriculturally active ingredient, the use of said compositions for treatment of plants and to methods for treating a plant by contacting the plant with a composition of the invention.
• WO 98/56825 relates to a hydrophobically modified anionic cellulose ether used in anti-settling, associative thickening, and in foam, emulsion, and suspension stabilizations, in a number of different industries, e.g. in a time-released application including pesticides.
• US 6,534,563 B1 relates to the use of compounds with particular elongational and flow viscosity as an anti-rebound agent included in aqueous plant protection formulations.
• the compounds used are selected from hydrosoluble or hydrodispersible surfactant polymers with a molecular weight in the range 5x10 5 to 5x10 6 g/mol, including polysaccharide derivatives, such as cellulose and its carboxyalkylated or hydroxyalkylated derivatives, wherein the alkyl portion contains 1 to 4 carbon atoms.
• WO 92/09197 relates to a herbicidal preparation comprising a polymeric stabiliser selected from a group of polymers all of which have a molecular weight of at least 7,000 Dalton, including hydrophobically modified non-ionic cellulose ethers.
• compositions comprising agriculturally active ingredients, which compositions have improved deposition properties.
• One object of the present invention is to provide alternative polymers as deposition enhancers for agriculturally active ingredients, usually pesticides and/or plant growth regulators.
• Another object of the invention is to provide compositions, preferably aqueous compositions, comprising the polymer and one or more agriculturally active ingredient.
• a non-ionic, water-soluble, hydrophobically modified lower alkyl hydroxyalkyl linear polysaccharide ether in particular a cellulose ether
• the hydrophobic group, with which the polysaccharide ether is hydrophobically modified comprises a long-chain C10-C18, preferably C12-C16, and most preferably C12-C14, alkyl or alkenyl group, preferably having a MS hyd rop h o b e of 0.001-0.02
• the lower alkyl group has 1-4 carbon atoms, preferably 1-2 carbon atoms, said group preferably having a DS a i ky i of 0.1- 2.5, more preferably 0.2-2.0, and most preferably 0.3-1.5
• the hydroxyalkyi groups are hydroxyethyl and/or hydroxypropyl preferably having a MS hy droxyaikyi of 0.2-4.0, exhibits
• a non-ionic, water-soluble, hydrophobically modified alkyl hydroxyalkyi linear polysaccharide ether in particular a cellulose ether, wherein the hydrophobic group, with which the polysaccharide ether is hydrophobically modified, comprises a long-chain C10-C18, preferably C12-C16, and most preferably C12-C14, alkyl or alkenyl group, preferably having a MS hy drophobe of 0.001-0.02; the lower alkyl group has 1-4 carbon atoms, preferably 1-2 carbon atoms, said group preferably having a DS a ik y i of 0.1-2.5, more preferably 0.2-2.0, and most preferably 0.3-1.5; and the hydroxyalkyi groups are hydroxyethyl and/or hydroxypropyl preferably having a MS hy droxyaikyi of 0.2-4.0; exhibits excellent properties as a deposition enhancer for agriculturally
• DS a ik y i, MS hy drophobe, and MShydroxyaikyi are used in their regular connotation, and give an overall account of the average number of the different substituents per anhydroglucose unit.
• DS the degree of substitution, is the average number of hydroxyl positions on the anhydroglucose unit that have been reacted, and can by definition vary between 0 and a maximum of 3.
• MS the molar substitution, is defined as the number of moles of reagent present per mole of anhydroglucose unit. This number could by definition be higher than 3.
• the newly formed hydroxyl group can further react with an additional alkylene oxide molecule. The process could then be repeated several times, forming polyoxyalkylene chains.
• the degree of substitution of hydroxyalkyi and alkyl groups can be determined by gas chromatography following degradation of the cellulose ether with HBr in glacial acetic acid, according to the procedure set out in Stead, J.B., & Hindley, H., (1969) "A modified method for the analysis oxyethylene/oxypropylene copolymers by chemical fission and gas chromatography" Journal of Chromatography, 42, 470-475.
• the linear polysaccharide ether contains the above-mentioned groups as ether substituents on the anhydroglucose units.
• the lower alkyl substituents are methyl, ethyl, propyl or butyl, or combinations thereof.
• the DS a ik y i which refers to the lower alkyl groups having 1-4 carbon atoms, is adapted to the hydrophobicity of these alkyl groups, which means that DS is normally lower for the more hydrophobic groups propyl and butyl than it is for methyl and ethyl.
• DS me th y i is suitably 0.3-2.5, preferably 0.5-2.0, and most preferably 0.7-1.9.
• DS e th y i is suitably 0.1-1.5, preferably 0.3-1.2, and most preferably 0.5-1.0.
• the hydroxyalkyl substituents are hydroxyethyl and/or hydroxypropyl, and optionally the linear polysaccharide ether, in particular cellulose ether, may further contain smaller amounts of hydroxybutyl substituents.
• the substituents and the degree of substitution are chosen so that the associative linear polysaccharide ethers, in particular cellulose ethers, of the invention become water-soluble.
• a product will be defined as water soluble, if after adding 1 g of product per litre water (0.1 % by weight) with stirring at 25°C, adjustment of the pH to a value of 6-7, using NaOH or HCI as appropriate, and after further stirring for 16 hours at said temperature, at least 20, preferably at least 40, more preferably at least 60, even more preferably at least 80 and most preferably at least 90% by weight of the product added is dissolved in the water.
• the MS hy droxyaikyi of the linear polysaccharide ether of the present invention may vary within wide limits but is normally within a range of 0.2-4.0, suitably 1.0-3.0, and preferably 1.5-2.8.
• the MShydroxyethyi is also normally within this general range.
• the MS h ydroxyprop y i is normally within a range of 0.1-2.0, suitably 0.2-1.7, and preferably 0.3-1.5. If hydroxybutyl groups are present, the MS hy droxybutyi is normally ⁇ 0.5.
• the longer hydrophobic groups are suitably derived from a glycidyl ether or a chloroglyceryl ether of a C10 to C18, preferably C12 to C16, and most preferably C12 to C14 alcohol that is preferably ethoxylated; from a C10 to C18, preferably C12 to C16, and most preferably C12 to C14 alkyl halide; or from a C12 to C20, preferably C14 to C18, and most preferably C14 to C16 a-olefin epoxide.
• the product typically has a MS hy drophobe of 0.001 or more, preferably 0.003 or more, and most preferably 0.005 or more.
• the MS hy drophobe is preferably 0.020 or less, more preferably 0.015 or less, and most preferably 0.010 or less.
• the linear polysaccharide ethers, in particular cellulose ethers, of the invention may be prepared by using known process steps (described e.g. in "Cellulose ethers" by T.G. Majewicz and T.J. Podlas in Kirk Othmer Encyclopedia of Chemical Technology, Vol. 5, pp. 445-466, online posting date: Dec. 4, 2000).
• alkali cellulose and suitable reactants can be reacted in the presence of an alkaline catalyst in order to introduce lower alkyl groups and hydroxyalkyl groups in such amounts that the intermediate cellulose ethers obtained are water-soluble.
• This intermediate cellulose ether product and a hydrophobic reactant having the formula
• R 1 is an alkyl or alkenyl group with 10-18, preferably 12-16, and most preferably 12-14 carbon atoms and z is a number between 0-10, preferably 1-5; or a reactant having the formula R 1 X (III), where X is a halide atom, are then reacted at an elevated temperature and in the presence of an alkaline catalyst to form a cellulose ether according to the invention.
• R 1 is an alkyl or alkenyl group with 10-18, preferably 12-16, and most preferably 12-14 carbon atoms.
• the hydrophobic reagents (I) and (II) are most preferred.
• the reagent used for hydrophobic modification may be added to an intermediate hydroxyethyl cellulose ether comprising an alkyl group with 1-4 carbon atoms, the alkyl group usually having a DS a i ky i of 0.1-2.5.
• the intermediate cellulose ether is made by adding ethylene oxide, optionally together with propylene oxide and/or butylene oxide, and an alkyl halide, such as methyl, ethyl, propyl or butyl chloride, to alkali cellulose.
• the intermediate cellulose ether that is used as starting material preferably has a cloud point of below 100°C and most preferably from 25°C to 85°C. More preferred is a route where the reagent used for hydrophobic modification, usually a lower akyl halide, and ethylene oxide are added to alkali cellulose, followed by a stepwise rising of the temperature.
• the cellulose ether is hydrophobically modified, for example by reacting the cellulose ether with an epoxide of formula (I) or a chloroglyceryl ether of formula (II) obtained from a fatty alcohol or an ethoxylated fatty alcohol via the epichlorohydrin route; from a long-chain alkyl halide of formula (III); or from an a- olefin epoxide of formula (IV).
• Suitable water-soluble nonionic cellulose derivatives that may be used as starting materials for the hydrophobically modified cellulose derivatives of the present invention are methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, propyl hydroxyethyl cellulose, butyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, and methyl hydroxyethyl hydroxypropyl cellulose.
• Preferred cellulose ethers are methyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, and ethyl hydroxyethyl cellulose.
• Suitable examples of long-chain alkylating reagents are hydrophobic epoxides or halides containing an alkyl or alkenyl group with 10 to 16 carbon atoms, such as dodecanol+2EO-glycidyl ether, tetradecanol+4EO-glycidyl ether, dodecyl bromide, and tetradecyl bromide.
• the hydrophobic alkylating agent can also be a mixture of compounds having different chain lengths.
• the cellulose ethers of the invention are polymers that may be represented by the structural formula
• R ce n is the residue of an anhydroglucose unit (C 6 H 10 O 5 ), and the separate R- groups may be the same or different and each R individually represents a substituent group of the formula (VI) given below, and n represents the degree of polymerisation (DP) and is usually an integer having a value of from about 500 to about 10,000.
• each R individually may be represented by a substituent group of the general formula
• R 1 is an alkyl or alkenyl group with 10-18 carbon atoms, preferably 12-16 carbon atoms, and most preferably 12-14 carbon atoms
• R 2 is an alkyl group with 1-4 carbon atoms or hydrogen.
• the cellulose ether as a whole should always comprise substituents where p and/or q are 2 or 3, where x is 1-2, and where m and/or t are >0.
• one specific hydroxyl group of the cellulose may react with one or several of the reagents.
• the hydroxyl group could first react with one or several ethylene oxide molecules, then there could be a further reaction with a compound of formula (I), followed by reaction with a C1-C4 alkyl halide.
• Another possibility would be a direct reaction with just one of the reactants mentioned above, or with any combination of two of them.
• no further substituents can be added to that position, since there will be no more hydroxyl group available to react with in that case.
• each anhydroglucose unit of the cellulose ether has a maximum of three positions that may be substituted, and the substituents R may be represented by the general formula (VI).
• the substituents for each specific anhydroglucose unit in the same cellulose molecule will obviously more or less differ from one another, and the formulae (V) and (VI) cannot by themselves adequately describe the polymer.
• the DS a ikyi, MS hy drophobe, and MShydroxyaikyi are normally used for this purpose, since these will give an overall account of the average number of the different substituents per anhydroglucose unit.
• a composition of the invention comprises at least one agriculturally active ingredient, usually a pesticide and/or a plant growth regulator.
• the agriculturally active ingredient is usually an organic, more usually synthetic, compound or mixture of such compounds.
• Pesticide refers to an organic compound which will prevent, destroy, repel or mitigate any pest. Pesticides contemplated for use in the present invention include fungicides, herbicides, insecticides, miticides, nematicides, acaricides, and molluscicides.
• plant growth regulator refers to an organic compound, which through physiological action will accelerate or retard the rate of growth or rate of maturation or otherwise alter the behaviour of ornamental or crop plants or the products thereof.
• Plant growth regulators contemplated for use in the present invention include abscisic acids, auxins, cytokinins and gibberellins.
• Preferred pesticides contemplated for use in the present invention include pesticides and plant growth regulators of the classes triazoles, strobilurins, alkylenebis(dithiocarbamate) compounds, benzimidazoles, phenoxy carboxylic acids, benzoic acids, sulfonylureas, triazines, pyridine carboxylic acids, neonicotinides, amidines, organophosphates, and pyrethroids, and salts and esters of the acid compounds.
• pesticides and plant growth regulators of the classes triazoles, strobilurins, alkylenebis(dithiocarbamate) compounds, benzimidazoles, phenoxy carboxylic acids, benzoic acids, sulfonylureas, triazines, pyridine carboxylic acids, neonicotinides, amidines, organophosphates, and pyrethroids, and salts and esters of the acid compounds.
• fungicides contemplated for use in the present invention includefungicides of the classes triazoles (e.g. tebuconazole, tetraconazole, cyproconazole, epoxiconazole, difenconazole, propiconazole, prothioconazole), strobilurins (e.g. trifloxystrobin, azoxystrobin, fluoxastrobin, pyraclostrobin), alkylenebis(dithiocarbamate) compounds (e.g. mancozeb) and benzimidazoles (e.g carbendazim).
• triazoles e.g. tebuconazole, tetraconazole, cyproconazole, epoxiconazole, difenconazole, propiconazole, prothioconazole
• strobilurins e.g. trifloxystrobin, azoxystrobin, fluoxa
• herbicides contemplated for use in the present invention includephenoxy carboxylic acids (e.g. 2,4-D-acid, MCPA), benzoic acids (e.g. Dicamba-acid), sulfonylureas (e.g. methylsulfuron-methyl, rimsulfuron), triazines (e.g. atrazine and simazine), triazolinones (e.g. amicarbazone) and pyridine carboxylic acids (e.g. triclopyr).
• MCPA methyl carboxylic acids
• benzoic acids e.g. Dicamba-acid
• sulfonylureas e.g. methylsulfuron-methyl, rimsulfuron
• triazines e.g. atrazine and simazine
• triazolinones e.g. amicarbazone
• pyridine carboxylic acids e.g. triclopyr
• insecticides contemplated for use in the present invention include neonicotinides (e.g. thiamethoxam, clothianidin, thiacloprid, dinotefuran, acetamiprid, nitenpyram, imidacloprid), amidines (e.g. amitraz), organophosphates (e.g. chlorpyrifos) and pyrethroids (e.g. permethrin, bifenthrin, deltamethrin).
• neonicotinides e.g. thiamethoxam, clothianidin, thiacloprid, dinotefuran, acetamiprid, nitenpyram, imidacloprid
• amidines e.g. amitraz
• organophosphates e.g. chlorpyrifos
• pyrethroids e.g. permethrin, bifenthrin, deltamethrin
• compositions of the invention may contain additional components.
• additional components include for example oils, co-solvents, and other adjuvants, such as surfactants, that are conventionally used to increase the bioefficacy of agricultural active ingredients.
• a composition according to the invention may be a so called "ready-to-use" composition, in which the polysaccharide ether and the agriculturally active ingredients are formulated in an aqueous medium to their intended end-use concentrations, i.e. the concentrations at which the composition is to be used.
• Such a ready-to-use composition usually comprises at least 0.005, preferably at least 0.01 , more preferably at least 0.02, still more preferably at least 0.03, and most preferably at least 0.04% (w/w) of the polysaccharide ether according to the invention, and at most 0.5, preferably at most 0.4, more preferably at most 0.3, even more preferably at most 0.2, still more preferably at most 0.18, still more preferably at most 0.15, and most preferably at most 0.1 % (w/w) of the polysaccharide ether according to the invention; and at least 0.005, preferably at least 0.01 , more preferably at least 0.02, and most preferably at least 0.03% (w/w) of the at least one agriculturally active ingredient, and at most 2, preferably at most 1 , more preferably at most 0.5, and most preferably at most 0.4% (w/w) of the at least one agriculturally active ingredient.
• a composition according to the invention may be a concentrated composition, a "pre-use" composition, in which the polysaccharide ether and the agriculturally active ingredient are formulated at a concentration higher than the intended end- use, optionally in a solvent different from water.
• a pre-use composition should preferably be diluted with an aqueous medium, usually water, before its end-use.
• the polysaccharide ether and the agriculturally active ingredient may also be available as separate articles, to be sold separate or together as a kit, which are to be mixed together to form an aqueous end-use formulation of the invention.
• the present invention further provides for a method for treating a plant, wherein the plant is contacted with a composition of the invention.
• the desired amount of agriculturally active ingredient to be contacted with a plant by means of such method depends on several parameters, such as the biological activity of the agriculturally active ingredient, but generally, the amount is adjusted to be sufficient for the agriculturally active ingredient to perform its desired activity.
• plant includes all parts of a plant, including roots, stems, leaves, flowers and fruits.
• any part of the plant such as a leaf, flower, fruit and/or stem of is contacted with a formulation of the present invention by means of spraying.
• the present invention relates to the use of a non-ionic, water- soluble, hydrophobically modified lower alkyl hydroxyalkyl linear polysaccharide ether as defined herein in connection to the composition of the invention, as a deposition enhancer for aqueous compositions comprising at least one agriculturally active ingredient.
• the present invention relates to a method for improving the deposition on a plant of an aqueous composition comprising at least one agriculturally active ingredient, the improvement comprising adding to the composition a non-ionic, water-soluble, hydrophobically modified lower alkyl hydroxyalkyl linear polysaccharide ether as defined herein in connection to the composition of the invention.
• the DP viscosity can be used to compare DP (degree of polymerisation) for different cellulose ethers, both hydrophobically modified and non-hydrophobically modified (see US 6,362,238 B2 and EP 1 694 711 B1).
• the DP viscosity can be measured using a conventional rheometer, such as a TA instruments AR-G2, using a 40 mm, 1 ° cone and plate measurement system, at a shear stress of 0.5 Pa and a temperature of 20°C.
• the DP viscosity is determined by dissolving the polymer in a solvent system consisting of 20% by weight of di(ethylene glycol) monobutyl ether and 80% by weight of water at 20°C. The viscosities obtained are then divided by a factor 2.7, in order to compensate for the higher viscosities obtained in an aqueous solution containing 20% by weight of di(ethylene glycol) monobutyl ether in comparison with the viscosities obtained in pure water.
• Natrosol 330C Plus is a cetyl ether of hydroxyethyl cellulose (HM-HEC) available from Aqualon.
• Example 1 Evaluation of polymers as deposition enhancers.
• a syringe is placed 0.5m above a flat surface.
• the droplets have a mean diameter of 2,800 ⁇ as determined by weighing 100 droplets and calculating the dimensions with the density of water.
• the flat surface which the droplets are landing on is covered with a layer of Parafilm (Pechiney Plastic Packaging Company), which mimics the hydrophobic leaf surface. The slope of this surface may be changed. The steeper the slope, the tougher it gets for the droplets to adhere to the surface. The slopes are reported in degrees, where 0 degrees means a horizontal surface and 90 degrees means a vertical
• Table 5 Deposition study of droplets at 0.04% concentration of polymers.
• non-ionic cellulose ethers are better than anionic cellulose ethers in terms of deposition properties. It is also concluded that cellulose ether derivatives containing both ethyl and hydroxyethyl substituents (EHEC) possess better deposition properties than cellulose ether derivatives containing only hydroxyethyl substituents (HEC). Further, it is concluded that hydrophobically modified EHECs possess better deposition properties than non-hydrophobically modified EHEC if the hydrophobic group is an alkyl group, but only marginally so if the hydrophobic group is a nonyl phenol group.
• EHEC ethyl and hydroxyethyl substituents
• the HM(C14)-EHEC was suspended in deionized water to a concentration of 0.2%w/w and thereafter swelled by the addition of ammonia to a pH above 8 and continuously stirred for an hour. Another sample of deionized water was saturated with an agriculturally active ingredient, and the pH of was adjusted to 7 and more agriculturally active ingredient was added until saturation. The agricultural active solution was filtered for solids and the solution was mixed in a ratio of 1 : 1 with the 0.2% HM(C14)-EHEC solution. The ready to use sample (0.1 %w/w HM(C14)- EHEC, 50% of the saturation level of active ingredient) was tested for the deposition angle according to the description in Example 1 above part.
• compositions of the invention deposited on the surface at an angle of 55°C.

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• Life Sciences & Earth Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• Agronomy & Crop Science (AREA)
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• Toxicology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
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• Dispersion Chemistry (AREA)

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